CN104345591A - Magnetic toner - Google Patents

Abstract

Provided is magnetic toner capable of favorably maintain fluidity of the magnetic toner in a developing unit even after a large number of image formation. The magnetic toner to which an external additive that has 1) a number average particle diameter of 70 or more and 200 or less, 2) a shape factor SF-1 of 100 or more and 250 or less, and 3) a shape factor SF-2 of 105 or more and 250 or less, is added, and a covering rate by silica on the surfaces of toner particles is 40.0% or more and 70.0% or less, and the magnetic toner has specific fluidity.

Description

Magnetic color tuner

Technical field

The present invention relates to the magnetic color tuner (hereinafter, can be called as " magnetic color tuner ") used in the image forming method and toner that realize electrophotographic image and electrostatic image spray.

Background technology

As usual, required that the magnetic color tuner for being formed by the image of magnetic mono-component jump development method has the high fluidity for the stable supplying of development sleeve, image color and image stabilization.As the external additive giving mobility, often use the external additive with small particle diameter.

Meanwhile, in recent years, for duplicating machine and printer etc., require more speed and more long-life, therefore need magnetic color tuner for being durable than use over a long time in the past.

Consider high speed and long-life further realization like this, expect that relying on magnetic color tuner to regulate between scraper plate at development sleeve and toner mutually than ever loads the communal space (share).Therefore, desirably promote the external additive with small particle diameter burying the surface adhering to magnetic color tuner underground further, and the function that will do not play as external additive.As a result, stably image color can not be kept by durable.

In addition, after using printer over a long time, and when the power supply of printer once turning off and be placed open again over a long time time, in developing cell, use the adjuvant of stirring vane to circulate become unstable, and relate to the image deflects of the first image after opening again, such as, due to the density unevenness one of the bad real picture black caused of development sleeve coating.

Jap.P. No.03684074 discusses the example buried underground suppressing the external additive in toner surface with small particle diameter by distortion silicon dioxide being added into non magnetic two-component developing agent toner.But when distortion silicon dioxide is applied to magnetic color tuner, that gives that charged development sleeve and toner regulate the friction between scraper plate to become than in dual component development is very strong.Therefore, there is the be full of cracks of external additive itself and cracked, and the reduction of the size of particle diameter.Therefore, external additive is embedded in toner, and occurs in the bad of permanance and adjuvant circulation aspect.

Japanese Patent Application Laid-Open No.2007-279702 discusses following example: be wherein desirably in the high sept effect in nonmagnetic toner, and when outside interpolation has the aspherical amorphous silica of Large stone thus obtains two-component developing agent, inhibit burying underground and rolling on the toner of the external additive caused owing to rubbing between developer.But when external additive being applied to magnetic mono-component skip philosophy, it is stronger that development sleeve and toner regulate between the friction ratio two-component developing agent between scraper plate.Therefore, the accumulation between the free and toner of external additive occurs, and can cause the first-class problem of such as informal voucher line and density unevenness.

Jap.P. No.4984619 discusses following example: wherein when together use have Large stone monodisperse spherical external additive and have in the magnetic color tuner of fine inorganic particles of small particle diameter, control powder rheometer (hereinafter, be abbreviated as FT-4) basic mobility energy time, transportation performance when toner being supplied to developing cell becomes good.But owing to carrying development sleeve and toner in rear developing cell to regulate the friction between scraper plate, monodisperse spherical external additive is also free at the rolls on surfaces of magnetic color tuner, and it can cause the pollution of charging member or the deterioration of developability in durable period.

In view of aforementioned aspect, there is the space to setting up durable stability and image quality improved stability in magnetic mono-component jump developing method.

Summary of the invention

The present invention is intended to the magnetic color tuner that can overcome above problem.

The present invention is intended to the magnetic color tuner in magnetic mono-component jump developing method with good durable stability.In addition, even if the present invention is intended to the magnetic color tuner that also can keep the mobility of magnetic color tuner in developing cell after great amount of images is formed well.

According to an aspect of the present invention, magnetic color tuner comprises the magnetic toner particle separately containing resin glue and magnetic material, and the first external additive, wherein

Described first external additive

1) be silica fine particles or resin combination-silica composite granules,

2) there is more than 70nm and the number average bead diameter of below 200nm,

3) more than 100 are had and a shape factor S F-1 of less than 250, and

4) more than 105 are had and a shape factor S F-2 of less than 250, and

The silicon dioxide coverage rate on the surface of the magnetic toner particle measured by ESCA is more than 40.0% and less than 70.0%, and

The gross energy calculated by rotary torque and vertical load is more than 80.0mJ and below 140.0mJ, and described rotary torque and described vertical load are obtained by following steps:

Described magnetic color tuner is positioned in measuring vessel;

To the described magnetic color tuner compacting in measuring vessel be positioned over by 5.8kPa load, and form the toner layer of compacting; With

Relative to the surface of the toner layer of described compacting, vertically pushed in the toner layer of described compacting by described propeller-type blade under constant speed, described propeller-type blade rotates under the peripheral speed of the outermost edge of 100mm/sec.

Description from following exemplary is become obvious by further feature of the present invention.

Embodiment

Various exemplary of the present invention, characteristic sum aspect will be described with reference to the accompanying drawings in detail.

Suppose the high speed of printer and long-life realization, require durable stability good than ever and image quality stability mutually.As the result of the present inventor's research, the durable stability found out that in magnetic mono-component jump developing method is relevant to toner deterioration greatly with image quality stability.As the result of further research, found out that the magnetic mono-component toner deterioration jumped in development depends on to have burying underground of the external additive of small particle diameter by what use the friction between the toner in the circulation of the adjuvant of stirring vane to cause in development sleeve in developing cell and the friction between toner adjustment scraper plate and developing cell greatly.As described above, because there is the deterioration of charged characteristic and the deterioration of mobility, when opening printer again after placing, the toner of deterioration causes the deterioration of image color and circulates bad.

Therefore, suppose the high speed of following printer etc. and long-life realization, importantly suppress the toner deterioration because development sleeve and toner regulate in the friction between scraper plate and developing cell the friction between the magnetic color tuner in using the adjuvant of stirring vane to circulate to cause.

Example for the technology suppressing described deterioration comprises a large amount of interpolations with the external additive of small particle diameter such as represented by silicon dioxide.But, when described technology gives life to durable stability, burying underground of the surperficial peripheral adjuvant of magnetic color tuner can not be avoided in Long-Time Service.As a result, be degrading mobility, result in the accumulation of magnetic color tuner powder bed in developing cell, it wields influence to image quality.

Selectively, in order to ensure stable mobility, the technology used together with the external additive with small particle diameter by the external additive with Large stone of the sept that can be used as between magnetic color tuner can be considered.But, when applying the preparing spherical SiO 2 produced by wet type sol-gel process as when there is the external additive of Large stone, because its spherical form is difficult to cause external additive to adhere to magnetic color tuner surface, and external additive is free from magnetic color tuner, and plays the function as sept by durable being not enough to.As a result, be degrading charged characteristic, and cause image bad, in addition, free external additive can pollute the charging member in developing cell.In addition, when the external additive with Large stone is at magnetic color tuner rolls on surfaces, therefore the external additive with small particle diameter used together is embedded in magnetic color tuner surface, is degrading mobility, and the accumulation of magnetic color tuner powder bed can be caused.

In order to deal with problems, use distortion silicon dioxide as the external additive by the sufficient sept effect of durable performance.But, because development sleeve and toner regulate the friction between scraper plate to cause the be full of cracks of external additive and cracked, and burying underground in toner surface can not be avoided.

As described above, in current condition, be difficult to suppress the toner by regulating the friction between the toner in the friction between scraper plate and developing cell in stirring vane to cause due to development sleeve in developing cell and toner to worsen the deterioration of charged characteristic and the deterioration of mobility that cause simultaneously.

Therefore, the present inventor thinks that the external additive with Large stone is important, it plays sufficient sept effect in durable period, even and if wherein because large stress such as development sleeve and toner regulate the friction between scraper plate, also there is not be full of cracks and cracked.In other words, the present inventor thinks can the simultaneously deterioration of inhibition zone electrical characteristics and the deterioration of mobility by external additive in durable period, and described external additive is not embedded in magnetic color tuner surface due to the friction in developing cell, do not roll and can not chap and cracked.

As the result of diligent studies, the present inventor has been found that to obtain by durable, to the suppression buried underground of magnetic toner particle peripheral adjuvant, play fully as the effect of sept with as the stable mobility of toner by the external additive not at magnetic color tuner surface scrolls, demand fulfillment following items.

Especially, importantly

(1) add external additive, it is silica fine particles or resin combination-silica composite granules, and has specified particle diameter and form factor,

(2) magnetic color tuner has controlled silicon dioxide coverage rate, and

(3) energy when the magnetic color tuner powder bed of compacting is loosened by propeller-type blade drops on specific scope.

First, the first external additive used in illustrative embodiments of the invention has more than 70nm and the number average bead diameter of below 200nm.

If number average bead diameter is less than 70nm, burying underground of the external additive that easy generation causes due to the friction in magnetic mono-component jump developing method between development sleeve and toner adjustment scraper plate.As a result, easily can not loosen the magnetic color tuner piled up, therefore, in real picture black, see informal voucher line or density unevenness one.On the other hand, if number average bead diameter is more than 200nm, then the effect as sept is played.But, the phase after endurance, the movement of external additive magnetropism toner recess and external additive from magnetic color tuner surface free together with occur, and see the pollution to charging member, and informal voucher line in real picture black and density unevenness one.In addition, the specific surface area of external additive becomes less, does not play effective electric charge and gives, and be degrading developability.

In addition, in an exemplary embodiment of the present invention, the shape factor S F-1 of the first external additive is more than 100 and less than 250, and SF-2 is more than 105 and less than 250.In addition, better is, and SF-1 is more than 140 and less than 250, and SF-2 is more than 120 and less than 250.

If the shape factor S F-2 of the first external additive is less than 105, then the shape of silicon dioxide becomes closer to spherical form, external additive becomes similar significantly to above to the movement of toner recess with free, and see the pollution to charging member, and informal voucher line in real picture black or density unevenness one.

On the contrary, if SF-1 is more than 250, then the major diameter of external additive is tending towards larger, is degrading mobility, and deterioration and the density unevenness one of image color occur.If SF-2 is more than 250, the degree of concavo-convex (unevenness) even becomes higher, and due to the be full of cracks of durable easy generation agglomerate particles, the size of particle diameter reduces, and buries underground.

In addition, in an exemplary embodiment of the present invention, the silicon dioxide coverage rate on the surface of magnetic toner particle is more than 40.0% and less than 70.0%.

If silicon dioxide coverage rate is less than 40.0%, there is the charged bad gathering therefore occurred between toner, and developability essential deterioration.On the contrary, if silicon dioxide coverage rate is higher than 70.0%, then hinder fixing.

In addition, in an exemplary embodiment of the present invention, the gross energy calculated by rotary torque and vertical load is more than 80.0mJ and below 140.0mJ.Described rotary torque and described vertical load are obtained by following steps:

Magnetic color tuner is positioned in measuring vessel;

To the magnetic color tuner compacting in measuring vessel be positioned over by 5.8kPa load, and form the toner layer of compacting; With

Relative to the surface of the toner layer of compacting, vertically pushed in the toner layer of compacting by propeller-type blade under constant speed, described propeller-type blade rotates under the peripheral speed of the outermost edge of 100mm/sec.The present inventor thinks described gross energy and regulate the friction between scraper plate by development sleeve and toner and be applied to the power of toner and be applied to the power of toner when the stirring vane of developing cell starts to rotate relevant.

If gross energy is less than 80.0mJ, then assemble in magnetic color tuner, and worsen initial developability, the reason that its concentration becoming real picture black worsens.Therefore, in real picture black, informal voucher line or density unevenness one is seen when restarting after stopping printer.

If gross energy is more than 140.0mJ, then initial developability is good, but piles up in developing cell due to durable, and becomes and be difficult in developing cell with stirring vane easily loosening toner.As a result, in real picture black, density unevenness one or informal voucher line is seen when opening printer again after stopping.

As described above, by using the external additive meeting all above features, can obtain by durable, do not cause external additive be embedded in magnetic color tuner, do not cause external additive magnetic color tuner rolls on surfaces and cause external additive to play fully as the effect of sept, and there is in any use the magnetic color tuner of steady flow.

Example as the silicon dioxide of the first external additive for illustrative embodiments of the invention comprises the wet silica by the preparation such as the precipitation method or sol-gel process, and passes through the dry silica of the preparation such as detonation method or vapor phase method.But dry silica is good, because the shape of the external additive of one of feature of the present invention easily controls.

The material of dry silica is silicon-halogen compound etc.

As silicon-halogen compound, use silicon tetrachloride.In addition, also independent silane compound can be used, such as methyl trichlorosilane, or trichlorosilane, or the admixture of silicon tetrachloride and silane compound is as material.

After described material gasification, described material is reacted with the water generated in oxyhydrogen flame as intermediate by flame hydrolysis, and obtains target silicon dioxide.

Such as, use the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and reaction equation is as follows:

SiCl ₄+2H ₂+O ₂→SiO ₂+4HCl

Hereinafter, will the method manufacturing the dry method aspherical silicon dioxide used in illustrative embodiments of the invention be described.

Oxygen is supplied to burner, start-up burner is lighted, then hydrogen be supplied to burner and form flame.Silicon tetrachloride as material is put into flame and gasified.Next step, carry out flame hydrolysis in the condition illustrated in Table 1, and collect the SiO 2 powder generated.

Mean grain size and shape at random can be regulated by retention time in the flame of silicon tetrachloride flow, oxygen supply flow rate, hydrogen supply flow rate and silicon dioxide.

Thereafter, the SiO 2 powder of acquisition is transferred to electric furnace, launches with thin layer approach, then heat-treat and sinter.

By application thermal treatment, improve coalescent intensity, and external additive regulates the friction between scraper plate to become durable for development sleeve in developing cell and toner, this is the feature of the dry method aspherical silicon dioxide used in illustrative embodiments of the invention.

In addition, also good be external additive is resin combination-silica composite granules.To describe in detail for the resin combination-silica composite granules in illustrative embodiments of the invention.

Resin combination-silica composite granules in illustrative embodiments of the invention has well and wherein uses resin particle as female particle and silica fine particles is present in the structure on the surface of resin particle.

The advantage of Composite can control shape to a certain extent.Be hydrophilic or hydrophobic according to resin combination and the compounding ratio of silica fine particles, the particle diameter of silica fine particles and silica fine particles, the shape of resin combination-silica composite granules can be controlled.

The example making the technology of compound with resin combination and silica fine particles is the method discussed in WO 2013/063291.Selectively, the example manufacturing the method for resin combination-silicon dioxide composite fine particles can be undertaken by following: i) then silica fine particles is injected to organic granular, and ii) resin dispersion be dissolved in solvent has been disperseed in the dispersion medium of silica fine particles wherein, granulation, then except desolventizing.

Example for the organic component of resin combination-silica composite granules comprises: styrene monomer such as styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to methoxy styrene and p-ethyl-styrene; Esters of acrylic acid is methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl, n-octyl, dodecyl acrylate, acrylic acid-2-ethyl caproite, octadecyl acrylate, acrylic acid-2-chloroethene ester and phenyl acrylate such as; Methyl acrylic ester is methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, lauryl methacrylate, methacrylic acid-2-Octyl Nitrite, octadecyl methacrylate, phenyl methacrylate, dimethylaminoethyl acrylate methyl base ammonia ethyl ester and methacrylic acid diethyl amino ethyl ester such as; With other monomer such as vinyl cyanide, methacrylonitrile and acrylamide.Can to use individually or can these monomers used in combination.As the silicon dioxide for resin combination-silica composite granules, the dry silica prepared by detonation method or vapor phase method etc. and be all applicable by wet silica prepared by sol-gel process.

In an exemplary embodiment of the present invention, compared with resin combination-silica composite granules, aspherical dry silica is better.This is because the shape controlling of aspherical dry silica is easier, and suppress easier by the resin fusion on the pollution of external additive free charging member caused from magnetic color tuner surface and drum.Especially, the silica composite granules that wherein multiple silica dioxide granule is coalescent is good.

In addition, as the first external additive in illustrative embodiments of the invention, can use and carry out surface treatment such as hydrophobization process or silicone oil and the silicon dioxide processed.

As methods of hydrophobilization, use with silicon dioxde reaction or physically absorb the organo-silicon compound of silicon dioxide thus chemically process silicon dioxide.Good method is the silicon dioxide generated by the gaseous oxidation of silicon halogen compounds with organo-silicon compound process.

In addition, such organo-silicon compound example is as follows: hexamethyldisilazane, trimethyl silane, trimethyl chlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, allyl phenyl dichlorosilane and benzyl dimethyl chlorosilane.

In addition, example comprises: bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three Organosilyl mercaptan, trimethyl silyl mercaptan and three Organosilyl acrylate.

Still further, example comprises: vinyl-dimethyl base acetoxylsilane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, diphenyl diethoxy silane and 1-HMDO.

Again further, example comprises: 1,3-divinyl tetramethyl disiloxane, 1,3-diphenyltetramethyl disiloxane and per molecule have 2 to 12 siloxane units and at the unit being arranged in end containing the dimethyl polysiloxane of hydroxyl being bonded to a Si atom.

These examples use individually or as two or more potpourris.

In addition, as the good silicone oil in the silicon dioxide of silicone oil process, the viscosity wherein at 25 DEG C is used to be 30mm ²/ more than s and 1,000mm ²the silicone oil of/below s.

Such as, the example of silicone oil comprises: the silicone oil of the silicone oil of dimethyl silicon oil, methyl phenyl silicone oil, α-methyl styrene modification, chlorphenyl silicone oil and fluorine richness.

The example of silicone oil disposal route is as follows:

Use mixer as the Henschel mixer directly silicon dioxide of mixing silane coupling agent process and the method for silicone oil,

Silicone oil is sprayed at as the method on the silicon dioxide of substrate, and silicone oil is dissolved or dispersed in suitable solvent, add and mixed silica and remove the method for desolventizing.

Better is the temperature silicon dioxide of silicone oil process being heated to more than 200 DEG C (more well, more than 250 DEG C) after silicone oil process in inert gas, and by the coating stable on surface.

Good silane coupling agent example comprises hexamethyldisilazane (HMDS).

For the toner-particle of 100.0 mass parts, these first external additives have more than 1.0 mass parts and the first external additive below 3.0 mass parts is better.

In addition, in the toner of illustrative embodiments of the invention, as the second external additive, good is uses to have and gives ability and more than 5nm and the inorganic fine powder of the primary particle number average bead diameter of below 30nm to the high fluidity of toner particle surf.

Such as, fine silica end can be used as the second external additive.The example at commercially available fine silica end comprises: AEROSIL130,200,300,380, TT600, MOX170, MOX80, COK84 (Aerosil Japan, Ltd.); Ca-O-SiL M-5, MS-7, MS-75, HS-5, EH-5 (Cabot Co.); Wacker HDK N20, V15, N20E, T30, T40 (Wacker-CHEMIE GMBH); D-C fine silica (Dow-Corning Corp.); With Fransol (Fransil Co.).

In addition, from the aggregation properties magnetic toner particle and charged characteristic, with due to the durable viewpoint buried underground caused, for the magnetic toner particle of 100 mass parts, second external additive is more than 0.1 mass parts and below 1.0 mass parts well, more well more than 0.5 mass parts and below 0.8 mass parts.

In addition, based on the content of the first external additive, toner contains more than 10 quality % and second external additive of below 50 quality % well.As long as meet with co-relation, the good characteristic easily loosened by stirrer paddle when toner can obtain about initial fluidity, charged characteristic and restart after durable period stops printer.

As needs, other external additive can be added in the toner of illustrative embodiments of the invention.

The example of other external additive comprises: release agent when charged auxiliary agent, conductivity-imparting agent, mobility donor, anti-caking agent, fixing hot-rolling, lubricant and as the resin fine particles of lapping compound and fine inorganic particles.

The example of lubricant comprises polyvinyl fluoride powder, zinc stearate powder and polyvinylidene fluoride powder.In them, polyvinylidene fluoride powder is good.

The example of lapping compound comprises ceria oxide powder, silicon carbide powder and strontium titanate powder.

In addition, in view of external additive is from the free of magnetic color tuner surface and the foundation easily being loosened both when restarting after placing developing cell over a long time by stirring vane, have more than 0.930 well and the average circularity of less than 0.960 for the magnetic color tuner in illustrative embodiments of the invention.

In addition, in view of the viewpoint of the control of the adhesion strength of the first external additive and the homogeneity of outside interpolation state, the magnetic toner particle of illustrative embodiments of the invention has more than 10.0nm and the average surface roughness of the magnetic toner particle of below 25.0nm well.The average surface roughness of magnetic toner particle represents the flatness on each magnetic toner particle surface.

< resin glue >

As the resin glue contained in magnetic toner particle, do not limit especially, but vibrin, vinyl group resin, epoxy resin or urethane resin can be used.

< magnetic material >

In an exemplary embodiment of the present invention, the example of the magnetic material contained in magnetic color tuner comprises: ferriferous oxide, such as magnetic iron ore, haematite and ferrite; Metal, such as iron, cobalt and nickel; The alloy type of the metals such as aforementioned metal and such as aluminium, cobalt, copper, lead, magnesium, tin, zinc, antimony, bismuth, calcium, manganese, titanium, tungsten and vanadium; With its potpourri.

These magnetic materials have the number average bead diameter of less than 2.0 μm well, well more than 0.05 μm and less than 0.5 μm.For the resin glue of 100 mass parts, the amount contained in toner is more than 40 mass parts and below 90 mass parts well.

< wax >

The magnetic color tuner of illustrative embodiments of the invention can contain wax.

Following instance is comprised for the wax in illustrative embodiments of the invention.The example of wax comprises: aliphatic chloroflo is low molecular weight polyethylene, low-molecular-weight polypropylene, polyolefin copolymer, polyolefin-wax, microcrystalline wax, paraffin and Fischer-Tropsch wax such as; The oxide such as oxidized polyethlene wax or its segmented copolymer of aliphatic series chloroflo; Vegetable wax is candelila wax, Brazil wax, lacquer tree fat and He Heba wax such as; Animal waxes is as beeswax, sheep oil and spermaceti; Mineral tallow is ceresine, ceresin and mineral tallow such as; The main wax containing aliphatic (acid) ester, such as montanic acid ester type waxes and castor wax; Wherein such as, by the wax of part or all of aliphatic (acid) ester deoxidation, deoxidation Brazil wax.In addition, described wax can be following among any: saturated straight chain fatty acids is as palmitic acid, stearic acid, montanic acid and the chain alkyl carboxylic acid with chain alkyl; Unsaturated fatty acid is brassidic acid, eleostearic acid and parinaric acid such as; Saturated alcohols such as octadecyl alcolol, eicosyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol and there is the alkylol of chain alkyl; Polyhydric alcohols is as sorbierite; Aliphatic amides is linoleamide, oleamide and lauric amide such as; The two stearic amide of saturated aliphatic acids bisamide such as di-2-ethylhexylphosphine oxide stearic amide, ethylenebis capric acid acidamide, ethylenebis lauric amide and hexa-methylene; Unsaturated fatty acid acid amides is ethylenebisoleaamide, hexa-methylene two oleamide, N, N '-two oil base hexane diacid acid amides and N, N '-two oil base decanedioic acid acid amides such as; The two stearic amide of aromatics bisamide such as m-xylene and N, N '-distearyl m-phthalic acid acid amides; Fat metallic salts is as calcium stearate, calcium laurate, zinc stearate and dolomol (being typically called as metallic soap); Wherein by vinyl monomer such as styrene and the acrylic acid-grafted wax to aliphatic chloroflo; The partial esterification products of fatty acid such as behenic acid monoglyceride and polyvalent alcohol; With the methyl ester compound with hydroxyl that the hydrogenation by vegetable oil obtains.

In addition, also use these waxes of molecular weight distribution pressurization-diaphoresis (pressing-sweating method), solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or the sharpening of fused junction crystallization well, and by these waxes of low-molecular-weight solid fatty acid, low-molecular-weight solid alcohol, low-molecular-weight solid chemical compound and other impurity removing.

Particular instance as the wax that can be used as release agent comprises: VISCOL (registered trademark) 330-P, 550-P, 660-P, TS-200 (from Sanyo Chemical Industries, Ltd. can buy); HIWAX400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (can buy from Mitsui Chemicals, Inc.); SASOL H1, H2, C80, C105, C77 (can buy from Schumann Sasol Co.); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (can buy from Nippon Seiro Co., Ltd.); UNILIN (registered trademark) 350,425,550,700, UNICID (registered trademark) 350,425,550,700 (can buy from Toyo-Petrolite Co., Ltd.); With haze tallow, beeswax, rice bran wax, candelila wax and Brazil wax (can buy from CERARICA NODA Co., Ltd.).

< charge control agent >

For in the magnetic color tuner in illustrative embodiments of the invention, good is by joint charge controlling agent and magnetic toner particle (internally adding charge control agent to magnetic toner particle), or passes through hybrid charge controlling agent and magnetic toner particle (externally adding charge control agent to magnetic toner particle) thus control the carried charge of magnetic toner particle and carried charge distributes to use charge control agent.

Comprise with the example of the negative charge controlling agent with negative charge for controlling toner: organometallic complex and chelate.The example of organometallic complex comprises: monoazo metal complex thing, cetylacetone metallic complex, aromatic hydroxycarboxylic acids metal complex and aromatic dicarboxylic acid metal complex.

In addition, the example of negative charge controlling agent comprises: aromatic hydroxycarboxylic acids, aromatic monocarboxylate, aromatic multi-carboxy acid and their slaine; With the acid anhydride of aromatic hydroxycarboxylic acids, aromatic monocarboxylate and aromatic multi-carboxy acid.

In addition, example comprises the ester compounds of aromatic hydroxycarboxylic acids, aromatic monocarboxylate and aromatic multi-carboxy acid, and phenol derivatives, such as bis-phenol.

The good example of electronegative negative charge agent comprises: Spilon Black TRH, T-77, T-95 (can buy from Hodogaya Chemical Co., Ltd.); With BONTRON (registered trademark) S-34, S-44, S-54, E-84, E-88, E-89 (can buy from Orient Chemical Industries Ltd.).

These charge control agents can use individually, or combinationally using as two or more type.In addition, also can use charge control resin, and can use together with above charge control agent.

Charge control agent uses well in fine grained mode.When these charge control agent inside are added into magnetic toner particle, the resin glue that good is for 100.0 mass parts, is added into magnetic toner particle by the charge control agent more than 0.1 mass parts and below 20.0 mass parts.

The magnetic toner particle used in illustrative embodiments of the invention can by comminuting method or polymerization manufacture.But, in view of shape controlling, be good by comminuting method manufacture.

In addition, above description toner constituent material is mixed fully by mixer such as bowl mill, then by heating and mixing machinery such as warm-up mill, kneader or extruder mixed material well, carry out after carrying out coarse crushing after cooled and solidified pulverizing and classification, and the method for carrying out the surface modification of magnetic toner particle with surface modification device is better.

The example of mixer comprises: Henschel mixer (manufacture of Mitsui Mining Co., Ltd.); Super mixer (Kawata Mfg.Co., Ltd. manufacture); Ribocone (Okawara Mfg.Co., Ltd. manufacture); Nauta mixer, Turbulizer and Cyclomix (Hosokawa Micron Corporation manufactures); Spiral pin mixer (manufacture of Pacific Machinery & Engineering Co., Ltd.) and Redige mixer (Matsubo Corporation manufactures).

The example of comminutor comprises: upstream injection grinding machine, Micron jet and Inomizer (Hosokawa Micron Corporation manufactures); IDS type grinding machine and PJM jet pulverizer (Nippon Pneumatic Mfg.Co., Ltd. manufacture); Crosswise jet grinding machine (Crossjet Mill) (Kurimoto, Ltd. manufacture); Ulmax (manufacture of Nisso Engineering Co., Ltd.); SK Jet-O-Mill (manufacture of Seisin Enterprise Co., Ltd.); Cliptron (Kawasaki Heavy Industries, Ltd. manufacture); Turbine type grinding machine (Turbo Mill) (manufacture of Turbo Kogyo Co., Ltd.) and Super Rotor (Nisshin Engineering Inc. manufactures).

In addition, the example of grader comprises: Classiel, Micron grader and Spedic grader (manufacture of Seisin Enterprises Co., Ltd.); Turbo classifier (manufacture of Nisshin Engineering Co., Ltd.); Micron seperator, Turboplex (ATP) and TSP seperator (manufacture of Hosokawa Micron Co., Ltd.); Elbow-Jet (manufacture of Nittetsu Mining Co., Ltd.); Dispersion seperator (manufacture of Japan Pneumatic Co., Ltd.) and YM Microcut (manufacture of Yasukawa Electric Co., Ltd.).

The example of surface modification device comprises: Faculty (Hosokawa Micron Corporation manufactures), mechanical fusion machine (Mechano Fusion) (Hosokawa Micron Corporation manufactures), Nobilta (Hosokawa Micron Corporation manufactures), hybridization machine (Hybridizer) (Nara Machinery Co., Ltd. manufacture), Inomizer (Hosokawa Micron Corporation manufactures), Theta Composer (Tokuju Corporation manufactures) and mechanical mill (Mechano Mill) (Okada Seiko Co., Ltd. manufacture).

In addition, the example screening the screening plant of coarse particle etc. comprises: Ultra Sonic (manufacture of Koei Sangyo Co., Ltd.); Resona Sieve and swinging sieving machine (Gyro Sifter) (Tokuju Corporation manufactures); Vibration ultrasonic system (Vibrasonic System) (Dalton Corporation manufactures); Supersonic cleaning machine (Soniclean) (manufacture of Sinto Kogyo Co., Ltd.); Turbine sieving machine (Turbo Screener) (manufacture of Turbo Kogyo Co., Ltd.); Micro sieving machine (Makino Mfg.Co., Ltd. manufacture) and circular shale shaker.

The magnetic toner particle of illustrative embodiments of the invention has more than 2.5 μm and the weight average particle diameter (D4) of less than 10.0 μm well.More well, more than 5.0 μm and less than 9.0 μm, and further more well, more than 6.0 μm and less than 8.0 μm.

In addition, by mixer such as Henschel mixer, the external additive describing expectation is above mixed fully, the magnetic color tuner according to illustrative embodiments of the invention can be manufactured.

Measure as follows according to the method for the physical property of the magnetic color tuner of illustrative embodiments of the invention.Example described below is in this way benchmark.

< measures the number average bead diameter of external additive and the method > of form factor

The measurement of the number average bead diameter of external additive is carried out with scanning electron microscope " S-4800 " (trade name, Hitachi, Ltd.).Observe the toner externally adding external additive wherein, be amplified in the visual field of 200,000 times the major diameter of 100 primary particles measuring external additive randomly, and obtaining number average bead diameter.Size according to external additive suitably regulates observation multiplying power.

By observing with scanning electron microscope (SEM) " S-4800 " (Hitachi, Ltd. manufacture) toner externally adding external additive wherein, following shape factor S F-1 and the SF-2 calculating external additive.

Magnitude according to external additive suitably regulates observation multiplying power.With image processing software " Image-Pro Plus5.1J " (MediaCybernetics manufacture), be amplified to the major diameter, girth and the area that calculate 100 primary particles in the visual field of 200,000 times.By shape factor S F-1 and the SF-2 of following formulae discovery individual particle, and use the mean value of 100 particles as the shape factor S F-1 of external additive and SF-2.

SF-1=(major diameter of particle) ²/ particle area × 100 × π/4

SF-2=(girth of particle) ²/ particle area × 100/4 π

< measures the method > of weight average particle diameter (D4)

By with high-accuracy domain size distribution measuring equipment " the Coulter Counter based on hole electric-resistivity method being provided with 100-μm of mouth pipe, Multisizer3 " (trade mark, Beckman Coulter, Inc. manufacture) and for arranging measuring condition and subsidiary special software " the Beckman-Coulter Multisizer3 of analysis to measure data, Version3.51 " (Beckman Coulter, Inc. produce), measure under 25000 effective Measurement channel numbers, measure the weight average particle diameter (D4) of the toner of illustrative embodiments of the invention, use special software analysis to measure data afterwards in described measurement thus calculate weight average particle diameter (D4).

As the electrolytic aqueous solution for measuring, the solution prepared to make solution concentration be about 1 quality % by dissolving superfine sodium chloride in ion exchange water can be used, such as " ISOTON II " (Beckman-Coulter, Inc. manufacture).

Before carrying out measuring and analyze, carry out the setting of special software as follows.

In special software " changing the interface of standard operating instructions (SOM) ", the tale of control model is set to 50,000 particle, measurement number of run is set to once, Kd value is placed through the value that use " 10.0-μm of standard particle " (Beckman-Coulter, Inc. manufacture) obtains.Measure button by pressing lower threshold value/noise level, threshold value and noise level are automatically set.Electric current is set to 1, and 600 μ A, are set to 2 by gain, electrolytic solution are set to ISOTON II, and mark measures the flushing of deutostoma pipe.

" that changes from pulse to particle diameter arranges interface " of special software, element spacing is set to logarithm particle diameter, particle diameter element is set to 256 particle diameter elements, and particle size range is arranged on the scope of 2 μm to 60 μm.

Specific measuring method is as follows.

(1) in the 250-ml glass round bottom beaker that Multisizer3 is special, place the electrolytic aqueous solution of about 200ml, beaker is placed on sample stage, and solution stirring rod is stirred in a counterclockwise manner under 24 revolutions per seconds.By " mouth rinses (flush of aperture) " function of analysis software, the dirt in removing mouth pipe and bubble.

(2) in 100-ml flat bottom glass beaker, place about 30ml electrolytic aqueous solution, and in this beaker, as spreading agent, additionally place the dilute solution (wherein " Contaminon N " is 10 quality % aqueous solution of the PH7 mild detergent for cleaning fine measuring instrument be made up of non-ionic surfactant, anionic surfactant and organic washing-assisting detergent, and Wako Pure Chemical Industries Ltd. manufactures) by doubly diluting " Contaminon N " and preparation by ion exchange water 3 quality of about 0.3ml.

(3) ion exchange water of scheduled volume is placed on ultrasonic disperse device " ultrasonic disperse system Tetora150 " (Nikkaki-Bios Co., Ltd. manufacture) tank in, described ultrasonic disperse device has the electric output power of 120W, is equipped with two embedded oscillators of the oscillation frequency of the 50kHz with 180 degree of phase offset therebetween, is then placed in this tank by above-mentioned for the about 2ml Contaminon N mentioned.

(4) beaker that above (2) are mentioned is placed in the beaker fixed orifice of ultrasonic disperse device, then makes ultrasonic disperse device operate.Then, maximum such mode is reached to regulate the height of beaker with the resonance state of the liquid level of electrolytic aqueous solution in beaker.

(5) under the condition of the electrolytic aqueous solution ultrasonic irradiation in the beaker that (4) describe more than inciting somebody to action, by about 10mg toner to be added into electrolytic aqueous solution on a small quantity and to be dispersed in wherein at every turn.Then, solution is proceeded further 60 seconds of ultrasonic disperse process.When carrying out ultrasonic disperse, the water temperature of tank is suitably adjusted to more than 10 DEG C and less than 40 DEG C.

(6) in the round bottom beaker being placed in the sample stage electrolytic aqueous solution instillation above (1) wherein disperseing to describe in (5) of toner described with transfer pipet, so that measure concentration and become about 5%.Then, carry out measuring until the granule number measured reaches 50,000.

(7) weight average particle diameter (D4) is calculated by the subsidiary special software analysis to measure data of equipment.When arranging figure/volume % in special software, in screen, " mean diameter " of analysis/volume statistical value (arithmetic mean) is weight average particle diameter (D4).

< measures the method > of toner average circularity

Measure the average circularity of toner-particle based on the condition of the measurement carried out in operation adjustment and analysis with streaming particle image analyser " FPIA-3000Model " (Sysmex Corporation manufactures).

Specific measuring method is as follows: first, and by about 20ml, therefrom the ion exchange water that impurity solid matter etc. removes to be placed in the container that glass makes by oneself in advance.About 0.2ml lean solution is added in this water as spreading agent, described lean solution is prepared by doubly diluting " Contaminon N " (10 quality % aqueous solution of the PH7 mild detergent for cleaning fine measuring instrument be made up of non-ionic surfactant, anionic surfactant and organic washing-assisting detergent are manufactured by Wako Pure Chemical Industries Ltd.) by ion exchange water about 3 quality.In addition, add about 0.02g and measure sample, subsequently by means of ultrasonic disperse machine dispersion treatment 2 minutes thus preparation measurement dispersion liquid.In this process, temperature dispersed system suitably being cooled consequently dispersion liquid becomes more than 10 DEG C and less than 40 DEG C.As ultrasonic disperse machine, use the desk-top supersonic cleaning machine dispersion machine (such as, " VS-150 ", Velvo-Clear Co. manufactures) that 50kHz oscillation frequency and 150W electricity export.The ion exchange water of scheduled volume is put into its tank, and above-mentioned for about 2ml CONTAMINON N is added in tank.

In the measurements, (multiplying power: 10 times that use has " UPlanApro ", opening number: 0.40) as the streaming particle image analyser of standard object lens, and use particle sheath (Particle Sheath) " PSE-900A " (Sysmex Corporation manufactures) as sheath solution.Dispersion liquid according to above procedure regulation is imported streaming particle image analyser, wherein measures 3000 toner-particles with HPF measurement pattern with tale pattern.Then, the threshold value of the binaryzation (binary-coded) during grain size analysis is set to 85%, and the particle diameter that will analyze is limited to more than 2.954 μm and is less than the equivalent circle diameter of 39.69 μm, and obtains the average circularity of toner-particle.

When measuring circularity, before starting measurement, with standard latex particle (such as, " research and test particle Latex Microsphere Suspensions5200A ", Duke Scientific Corporation manufactures, and dilutes with ion exchange water) carry out auto-focusing control.Therefore, measure after starting, advantageously can carry out auto-focusing control every 2 hours.

In the embodiment of the present application, use and its correction operated by Sysmex Corporation and is awarded the streaming particle image analyser of the correction certificate issued by Sysmex Corporation.Being limited to more than 2.954 μm except the particle diameter that will analyze and being less than except the equivalent circle diameter of 39.69 μm, measuring under the measurement arranged when accepting correction certificate and analysis condition.

The measurement > of the average surface roughness of < magnetic toner particle

In an exemplary embodiment of the present invention, the average surface roughness of magnetic toner particle is measured with scanning probe microscopy.The example of measuring method illustrates as following.

Probe station: SPI3800N (manufacture of Seiko Instruments Co., Ltd.).

Measuring unit: SPA400

Measurement pattern: DFM (resonance mode) configuration picture picture

Cantilever: SI-DF40P

Resolution: X data number 256

Y data number 128

In an exemplary embodiment of the present invention, the surface of the magnetic toner particle of 1 μm of area is measured.The area measured is 1 μm of area of the core of the magnetic toner particle measured by scanning probe microscopy.As the magnetic toner particle that will measure, at random select and measure the magnetic toner particle of the weight average particle diameter (D4) equaling to be measured by coulter counter method.The data of measurement are carried out secondary correction.Measure more than 5 different magnetic toner particle, calculate the mean value of the data obtained, and use the value that calculates as the average surface roughness of magnetic toner particle.

Wherein external additive being externally added in the magnetic color tuner of magnetic toner particle, when measuring magnetic toner particle surperficial with scanning probe microscopy, needing to remove external additive.The example of ad hoc approach is as follows:

(1) 45mg magnetic color tuner is put into sample bottle, and add 10ml methyl alcohol.

(2) sample supersonic cleaning machine is disperseed 1 minute, and separate external adjuvant.

(3) absorption and filtered sample (10 μm of membrane filters), and be separated magnetic toner particle and external additive.

Selectively, magnet is placed to the bottom of sample bottle.Fixed magnetic toner-particle, and only supernatant can be separated.

(4) above step (2) and (3) are carried out total three times, and by room temperature dry fully for the magnetic toner particle vacuum dryer obtained.

The magnetic toner particle of external additive has therefrom been removed with sem observation.Confirm external additive not the fact after, the surface of magnetic toner particle can be observed with scanning probe microscopy.When removing external additive not yet fully, step (2) and (3) are repeatedly carried out until remove external additive fully.Then, the observation on the surface of magnetic toner particle is carried out with scanning probe microscopy.

The example of the other method of the removing external additive of (2) and (3) is replaced to comprise the method for dissolving external additive with alkali.As alkali, sodium hydrate aqueous solution is good.

Following term will be described.

Average surface roughness (Ra)

In order to be applied to measured surface, this is the three-dimensional expansion of the center line average roughness (Ra) defined in JIS B0601.It is the mean value from standard surface to the absolute value of designated surface deviation, and it is represented by following formula:

[formula 1]

$\mathrm{Ra}=\frac{1}{S_0}{\&Integral;}_{T_B}^{Y_T}{\&Integral;}_{X_L}^{X_R}|F(X,Y)-Z_0|\mathrm{dXdY}$

F (X, Y): the surface indicated by whole measurement data

S ₀: the area when hypothesis designated surface is smooth ideally

Z ₀: the mean value of Z data in designated surface

In illustrative embodiments of the invention, designated surface means the 1 μm of foursquare area that will measure.

< measures the method > of silicon dioxide coverage rate

First, measured by X-ray photoelectron spectroscopic analysis (ESCA) and derive from silicon dioxide and the amount being present in silicon on toner particle surf (hereinafter, Si is made in abbreviation).

ESCA instrumentation and testing condition is as follows.

Use instrument: the Quantum2000 that ULVAC-PHI, Incorporated manufacture

Analytical approach: narrow analysis

Measuring condition:

X-ray source: Al-K α

X-ray: beam diameter 100 μm, 25W, 15kV

Photoelectron incident angle: 45 °

Logical energy (Pass energy): 58.70eV

Measurement range:

In analytical approach, first, the peak deriving from the C-C key of carbon atom 1s track is corrected to 285eV.Subsequently, with ULVAC-PHI, the relative sensitivity factors that Incorporated provides, by wherein at more than 100eV and the peak area deriving from silicon atom 2p track of summit that detects of below 105eV, calculate derive from silicon dioxide Si relative to the ratio " A (atom %) " of the total amount of constitution element in toner.

Next step, by the method similar to method described above, measure the Si amount being applied to the independent silicon dioxide of magnetic color tuner, and acquisition derives from the ratio " B (atom %) of Si relative to the total amount of constitution element in independent silicon dioxide of silicon dioxide.This ratio B (atom %) is considered to the value of coverage rate 100%.

Now, by the silicon dioxide coverage rate in following calculating illustrative embodiments of the invention:

Silicon dioxide coverage rate (%)=ratio A/ ratio B × 100

When the first external additive and the second external additive are all silicon dioxide, the independent Si amount of the first external additive and the external additive of the second external additive is identical, and is measured by above method.

On the other hand, when using element in addition to silica as the first external additive, the Si amount that the external additive of the first and second external additives is independent is different, therefore calculates with following methods.

Measure the ratio A of the Si in the magnetic color tuner only adding the first external additive ₁.Similarly, the ratio A of the Si in the magnetic color tuner only adding the second external additive is measured ₂.By the ratio " B (atom %) " of Si, the silicon dioxide coverage rate by this situation of following formulae discovery:

Silicon dioxide coverage rate (%)=(ratio A ₁/ ratio B+ ratio A ₂/ ratio B) × 100

< measures the method for FT-4 and calculates the method > of gross energy

In an exemplary embodiment of the present invention, the energy when loosening the toner powder layer at compaction state is measured with the powder flowbility analyser (FT-4, Freeman Technology manufactures) being equipped with rotating screw paddle type blade.

Especially, measured by following operation.In all operations, the propeller-type blade of use is the 23.5mm diameter propeller for FT-4 test.Turning axle is present in the normal direction at 23.5mm × 6.5mm vane plate center.Vane plate is successfully rotated counterclockwise 70 ° and be successfully rotated counterclockwise 35 ° in the part of distance turning axle 6mm in its two outermost edge part.Blade material is SUS stainless steel.

(1) first, by being placed on 23 DEG C, in 60% environment, the 23g toner of 3 days is placed to the (separation container (model: C4031) of diameter 25mm, volume 25mL in the special container measured for FT-4, container bottom is about 51mm to the height of separate section, hereinafter, can be called as simply " container ").

(2) operation is adjusted

A () is by surface (edge wherein blade rotary does not push the direction of the magnetic color tuner powder bed) rotation clockwise relative to magnetic color tuner powder bed of the blade speed (peripheral speed in blade ragged edge edge) of propeller blade 60mm/sec.Propeller blade is advanced into the position of the bottom surface 10mm from toner powder layer from powder bed surface, wherein wherein by speed that the track of the ragged edge edge spike of blade during movement and the surperficial angle (hereinafter, can be called as " blade-shaped angulation ") formed of powder bed are 5 degree along the fltting speed in the direction vertical with magnetic color tuner powder bed.

B () subsequently, when rotating along the clockwise direction relative to powder bed surface under the blade speed at 60mm/sec, propeller blade is advanced into the position of the bottom surface 1mm from magnetic powder last layer, the fltting speed wherein along the vertical direction of powder bed wherein forms the speed that angle becomes 2 degree.

C () subsequently, when rotating along the counter clockwise direction relative to toner powder layer surface under the blade speed at 60mm/sec, under formation angle is the withdrawal speed of 5 degree, propeller-type blade is moved to the position of the bottom surface 70mm from powder bed, and extract toner powder layer out.

(d) once complete and recall, by blade along clockwise and alternately to rotate so that abate is attached to the toner of blade counterclockwise on a small quantity.

E () subsequently, repeats the operation of (a) to (d), and will adjust operation and carry out total five times.

(3) compacting operation of magnetic color tuner

Compaction test piston (diameter 24mm, height 20mm and engagement bottom) is installed and replaces propeller-type blade, and carry out the compacting 60 seconds of powder bed with 5.8kPa.

(4) cutting operation

The toner powder layer of the cutting part at FT-4 measurement special container is struck off, and the toner of removing at toner powder layer top, so that form the toner powder layer with same volume (25mL).

(5) operation is measured

By the blade speed of propeller-type blade 100mm/sec, turn clockwise relative to the surface of magnetic color tuner powder bed.Fltting speed along the vertical direction of magnetic color tuner powder bed to be the angle (hereinafter, can be called as " blade track angle ") wherein formed by the track of the ragged edge edge spike of blade during movement and powder bed surface the be speed of 5 degree.Under this condition, with the position of the bottom surface 70mm from magnetic color tuner powder bed as measurement starting point, propeller-type blade is advanced into the position of the bottom surface 10mm from magnetic powder last layer.In addition, the scope of about first 20mm after measuring from the position from bottom surface 70mm is the wherein non-existent scope of magnetic color tuner layer, and is carry out the region of dallying close to magnetic color tuner layer from blade simultaneously.

Measure in operation above, by being the gross energy defined illustrative embodiments of the invention when the value that propeller-type blade is calculated from the rotary torque obtained during the position that measurement starting point is advanced into from bottom surface 10mm and vertical load.

Basic comprising and the feature of illustrative embodiments of the invention have below been described.With reference to following examples, exemplary of the present invention will be described particularly.But exemplary of the present invention is not implemented example restriction.In embodiment, unit is mass parts.

The Production Example > of < external additive A

Oxygen is supplied to burner, start-up burner is lighted, then hydrogen be supplied to burner and form flame.Silicon tetrachloride as material is put into flame and gasified.Carry out flame hydrolysis under the condition illustrated in Table 1, and collect the SiO 2 powder generated.

Thereafter, the SiO 2 powder of acquisition is transferred to electric furnace, launches with thin layer approach, heat-treat at 700 DEG C, then sinter and assemble.

Next step, apply hydrophobization process so that the hexamethyldisilazane of 10 mass parts be added into the silica fine particles of the acquisition of 100 mass parts as surface conditioning agent.

The Production Example > of < external additive B to E

Except such as changing except silicon tetrachloride flow, oxygen supply flow rate, hydrogen supply flow rate, silica concentration and retention time shown in table 1, with the first external additive A similarly, obtain the first external additive B to E.The number average bead diameter of external additive A to E and form factor are as shown in table 2.

[table 1]

The manufacturing condition of the aspherical dry silica as external additive used in illustrative embodiments of the invention

The Production Example > of < external additive F

As the external additive F of physical property with table 2, prepare the external additive manufactured according to the embodiment 1 of WO 2013/063291.

The Production Example > of < external additive G

Except not carrying out, except sintering thermal treatment, obtaining external additive G by the operation similar to external additive A.Number average bead diameter shown in table 2 and form factor.

The Production Example > of < external additive H, I and J

External additive H, I and J is obtained so that the surface hexamethyldisilazane of the silica fine particles obtained by typical wet type sol-gel process is carried out the such mode of hydrophobization process.Number average bead diameter shown in table 2 and form factor.

< external additive K>

As external additive K, use commercially available strontium titanates (manufacture of Fuji Titanium Industry Co., Ltd.).Number average bead diameter shown in table 2 and form factor.

< external additive L>

As external additive L, use the silicon dioxide obtained by vapor phase method, wherein BET specific surface area is 200m ²/ g and primary particle size is 13nm.

< external additive M>

As external additive M, use the silicon dioxide obtained by vapor phase method, wherein BET specific surface area is 300m ²/ g and primary particle size is 10nm.

[table 2]

The manufacture > of < magnetic toner particle 1

Above material is mixed in advance with Henschel mixer.Afterwards, by potpourri with being heated to the biaxial extruder melting of 110 DEG C and mixing.Mixing thing is cooled, then uses hammer-mill coarse crushing, and obtain the product of the coarse crushing of toner.Use mechanical crusher turbine type grinding machine (Turbo Kogyo Co., Ltd. manufacture, surface (plated thickness is 150 μm and skin hardness is HV1050) with the evanohm plating rotor containing chromium carbide and stator), the product of the coarse crushing of acquisition is carried out fine powder by mechanical crushing broken.In the fine powder pulverized powder obtained, by fine grained and coarse particle by means of multi-level hierarchical equipment (the elbow nozzle grader (Elbow Jet Classifier) utilizing Coanda effect, Nittetsu Mining Co., Ltd. manufactures) remove with time stage.After classification, use surface modification device: Faculty F-600 (Hosokawa Micron Corporation manufactures) carries out the process on magnetic toner particle surface, and carry out surface modification and fine grained removing.As shown in table 3, obtained the magnetic toner particle 1 with the average surface roughness (Ra) of the weight average particle diameter (D4) of 7.2 μm, the average circularity of 0.944 and 23.9nm by above technique.

The Production Example > of < magnetic toner particle 2

Except the revolving circumferential velocity of the dispersion rotor of elevation surface reforming apparatus, with the Production Example of magnetic toner particle 1 similarly, obtain the magnetic toner particle 2 with the average surface roughness (Ra) of the weight average particle diameter (D4) of 6.9 μm, the average circularity of 0.957 and 10.6nm.

The Production Example > of < magnetic toner particle 3

Do not use except mechanical crusher except using injection stream comminutor, with magnetic toner particle 1 similarly, obtain and there is the magnetic toner particle 3 of the average surface roughness (Ra) of the weight average particle diameter (D4) of 6.8 μm, the average circularity of 0.937 and 31.5nm.

The Production Example > of < magnetic toner particle 4

Except not carrying out the surface modification of use surface modification device, with the Production Example of magnetic toner particle 1 similarly, obtain the magnetic toner particle 4 with the average surface roughness (Ra) of the weight average particle diameter (D4) of 7.1 μm, the average circularity of 0.925 and 51.2nm.

The manufacture method > of < magnetic toner particle 5

By the 0.1mol/L-Na of 450 mass parts ₃pO ₄aqueous solution import the ion exchange water of 720 mass parts, and solution is heated to the temperature of 60 DEG C.Thereafter, by the 1.0mol/L-CaCl of 67.7 mass parts ₂aqueous solution be added into wherein thus obtain containing dispersion stabilizer (Ca ₃(PO ₄) ₂) aqueous medium.

(saturated polyester resin obtained by the condensation reaction between the ethylene oxide adduct of bisphenol-A and terephthalic acid (TPA), Mn=5,000, acid number=12mg KOH/g and Tg=68 DEG C)

Component masher described above (Mitsui Miike Engineering Corp. manufactures) is disperseed equably and mixes thus produce monomer composition.Monomer composition is heated to 60 DEG C, 15.0 mass parts paraffin (temperature of heat absorption summit: 77.2 DEG C) are mixed with monomer composition and is dissolved in wherein, then 4.5 mass parts polymerization initiator 2,2'-azos two (2,4-methyl pentane nitrile) are dissolved in potpourri.

Monomer composition is imported in aqueous medium described above, and at 60 DEG C N ₂under 12,000rpm, 15 minute granulation is carried out by stirring the mixture with Clearmix (M Technique Co., Ltd.) under atmosphere.Then, when stirring with oar stirring vane, under 0.5 DEG C/min of speed, mixture temperature is increased to 70 DEG C, and at 70 DEG C, carries out reaction 5 hours.Subsequently, be warming up to 90 DEG C, and keep 2 hours.After having reacted, cooling suspension, adds hydrochloric acid and dissolves Ca ₃(PO ₄) ₂, and carry out filtering, washing with water and drying, as shown in table 3, obtain the magnetic toner particle 5 with the average surface roughness (Ra) of the weight average particle diameter (D4) of 8.0 μm, the average circularity of 0.979 and 2.8nm.

[table 3]

The physical property of magnetic toner particle

< embodiment 1>

The external additive L Henschel mixer as the second external additive of the external additive A as the first external additive of 1.8 mass parts and 0.5 mass parts is externally mixed in the magnetic toner particle 1 of 100 mass parts, potpourri is divided with there being the mesh screen in 100 μm of apertures, and obtains the magnetic color tuner 1 with negative friction charged characteristic.The physical property of the magnetic color tuner 1 obtained shown in table 4.Following evaluation is carried out with the toner obtained.

[evaluation]

Consider the more speed of printer and more long-life further realization, transformation HP LaserJet Enterprise600 M603dn is to have the processing speed of 400mm/s and to use.

982g magnetic color tuner 1 is inserted predetermined handle box.With machine wherein two have printing rate be 2% vertical line pattern be a job work between stop once, then start the pattern that the such mode of next work arranges and carry out image output test.In addition, as the evaluation environment of image output test, ambient temperature and moisture environment (23 DEG C, 60%RH) is used.

Real picture black concentration

After exporting 100 paper, with output 50, after 000 paper, the chart that wherein real picture black portion is formed on whole printer paper is exported one by one, and be used as the Macbeth densimeter (Macbeth Co. manufactures) of the reflection of the concentration using SPI wave filter, measure reflection density at 5 places, and obtain its mean value.Numerical value shows that more greatly developability is better.Evaluation result shown in table 5.Evaluation criterion is as follows:

A: image color is more than 1.45

B: image color is more than 1.40 and is less than 1.45

C: image color is more than 1.30 and is less than 1.40

D: image color is less than 1.30

Homogeneity (real black density unevenness one) in real blackboard

After exporting 25,000 paper, under ambient temperature and moisture environment (23 DEG C, 60%RH), close the power supply of image forming apparatus, and image forming apparatus is placed one week.Then, open image forming apparatus again, export a piece of paper wherein real picture black portion being formed at the chart on whole printer paper, and be used as the Macbeth densimeter (Macbeth Co. manufactures) of the reflection of the concentration using SPI wave filter, measure reflection density at 5 places.In order to its mean value of upper standard evaluation, and obtain the difference in 5 measured values between maximal value and minimum value.This difference is evaluated in following standard.Evaluation result shown in table 5.

More than A:0.00 and be less than 0.10

More than B:0.10 and be less than 0.15

More than C:0.15

Informal voucher line (real black and white strip) in real blackboard

After exporting 25,000 paper, under ambient temperature and moisture environment (23 DEG C, 60%RH), close the power supply of image forming apparatus, and image forming apparatus is placed one week.Then, then open image forming apparatus, export a piece of paper wherein real picture black portion being formed at the chart on whole printer paper, and evaluate in order to lower standard.Evaluation result shown in table 5.

A: have no informal voucher line vertical line

B: see one or two informal voucher line vertical line slightly

C: see informal voucher line vertical line clearly, or see the vertical line of more than three slightly

Charging member pollutes

After exporting 50,000 paper, collect the charging member in developing cell, whether visiblely with the naked eye detect the dirt deriving from external additive, and evaluate in order to lower standard.Evaluation result shown in table 5.

A: have no white dirt.

B: see some white dirts slightly.

C: white dirt is given prominence to.

< embodiment 2 to 14 and comparative example 1 to 11>

Except changing to except the formula shown in table 4 by formula, similar in appearance to embodiment 1, obtain magnetic color tuner 2 to 25.The physical property of the magnetic color tuner obtained shown in table 4.

In addition, the evaluation similar in appearance to embodiment 1 is carried out with the magnetic color tuner 2 to 25 obtained.Evaluation result shown in table 5.

[table 4]

The formation of magnetic color tuner and physical property

[table 5]

Evaluation result

Although reference example embodiment describes the present invention, be appreciated that the present invention is not restricted to disclosed exemplary.The scope of following claim is explained meeting the most widely to contain all this type of amendment and equivalent 26S Proteasome Structure and Function.

Claims (4)

1. a magnetic color tuner, it comprises:

Contain the magnetic toner particle of resin glue and magnetic material separately; With

First external additive,

Wherein said first external additive

1) be silica fine particles, or resin combination-silica composite granules,

2) there is more than 70nm and the number average bead diameter of below 200nm,

3) more than 100 are had and a shape factor S F-1 of less than 250, and

4) more than 105 are had and a shape factor S F-2 of less than 250, and

The silicon dioxide coverage rate on the surface of the described magnetic toner particle measured by X-ray photoelectron spectroscopic analysis (ESCA) is more than 40.0% and less than 70.0%, and

The gross energy calculated by rotary torque and vertical load is more than 80.0mJ and below 140.0mJ,

Described rotary torque and described vertical load are obtained by following steps:

Described magnetic color tuner is positioned in measuring vessel;

To the described magnetic color tuner compacting in measuring vessel be positioned over by 5.8kPa load, and form the toner layer of compacting; With

Relative to the surface of the toner layer of described compacting, vertically pushed in the toner layer of described compacting by propeller-type blade under constant speed, described propeller-type blade rotates under the peripheral speed of the outermost edge of 100mm/sec.

2. magnetic color tuner according to claim 1, the average circularity of wherein said magnetic toner particle is more than 0.930 and less than 0.960.

3. magnetic color tuner according to claim 1, wherein said magnetic color tuner contain there is more than 5nm and the silicon dioxide of the primary particle number average bead diameter of below 30nm as the second external additive, and

The content of described second external additive

I) relative to the described magnetic toner particle of 100 mass parts, be more than 0.1 mass parts and below 1.0 mass parts, and

Ii) based on the content of described first external additive, be more than 10 quality % and below 50 quality %.

4. magnetic color tuner according to claim 1, wherein said first external additive is the silica composite granules of wherein coalescent multiple silica dioxide granule.